Abstract

AbstractPolarographic catalytic wave of chlordiazepoxide in the presence of K2S2O8 was studied in aqueous and DMF/H2O mixed solutions. The results showed that a single reduction wave in alkaline medium was the reduction of the N = C bond in 1,2‐position of chlordiazepoxide via an intermediate free radical in two one‐electron successive additions. When K2S2O8 was present, the free radical of the N = C bond was oxidized to regenerate the original, producing a parallel catalytic wave of chlordiazepoxide. It was determined that the apparent rate constant kf of the oxidation reaction was 3.2 × 103 mol−1·L·s−1. Using the catalytic wave the trace of chlordiazepoxide can be determined by linear‐potential scan polarography. In NH3/NH4Cl (pH 10.2 ± 0.1, 0.12 mol/L)/K2S2O8(0.016 mol/L) supporting electrolyte, the second‐order derivative peak current of the catalytic wave was rectilinear to chlordiazepoxide concentration in the range of 3.20 × 10−8‐1.60 × 10−7, 1.60 × 10−7‐1.44×10−6 and 1.44×10−6‐1.44x 10−5 mol/L, respectively. The limit of detection was 9.0×10−9 mol/L.

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